Hydrogenated TiO2 Nanorod Arrays Decorated with Carbon Quantum Dots toward Efficient Photoelectrochemical Water Splitting

  • Zhao Liang
    Zhao Liang
    School of Materials Science and Engineering, Hunan University, Changsha City 410082, P.R. China
    Institute of Materials, Ningbo University of Technology, Ningbo City 315211, P.R. China
    More by Zhao Liang
  • Huilin Hou
    Huilin Hou
    Institute of Materials, Ningbo University of Technology, Ningbo City 315211, P.R. China
    More by Huilin Hou
  • Zhi Fang
    Zhi Fang
    Institute of Materials, Ningbo University of Technology, Ningbo City 315211, P.R. China
    More by Zhi Fang
  • Fengmei Gao
    Fengmei Gao
    Institute of Materials, Ningbo University of Technology, Ningbo City 315211, P.R. China
    More by Fengmei Gao
  • Lin Wang
    Lin Wang
    Institute of Materials, Ningbo University of Technology, Ningbo City 315211, P.R. China
    More by Lin Wang
  • Ding Chen*
    Ding Chen
    School of Materials Science and Engineering,  State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body, College of Mechanical and Vehicle Engineering, Hunan University, Changsha City 410082, P.R. China
    *E-mail: [email protected] (D.C.).
    More by Ding Chen
  • , and 
  • Weiyou Yang*
    Weiyou Yang
    Institute of Materials, Ningbo University of Technology, Ningbo City 315211, P.R. China
    *E-mail: [email protected] (W.Y.).
    More by Weiyou Yang
Cite this: ACS Appl. Mater. Interfaces 2019, 11, 21, 19167–19175
Publication Date (Web):May 6, 2019
Copyright © 2019 American Chemical Society
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Supporting Info (1)»


Limited light harvesting and charge collection are recognized as grand challenges for the exploration of highly efficient TiO2 photoanodes. To overcome these intrinsic shortcomings, we reported the designed photoanode based on TiO2 nanoarrays with both hydrogenation treatment and surface decoration of carbon quantum dots (CQDs) toward efficient photoelectrochemical water splitting. The results revealed that hydrogenation treatment could cause the formation of oxygen vacancies to suppress the recombination of photoinduced carriers. Meanwhile, the decorated CQDs could not only play as the electron reservoirs to trap photoinduced electrons but also remarkably enhance the solar light harvesting due to their upconversion effect. The as-fabricated photoanodes exhibited a large photocurrent density of ∼3.0 mA/cm2 at 1.23 V versus reversible hydrogen electrode under simulated sunlight, which was the highest one among hydrogenated TiO2 photoanodes ever reported and was ∼6 times that of pristine analogues.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.9b04059.

  • Microstructural characterizations, UV–vis spectra, and PEC performances of CQDs, pristine TiO2, CQDs/TiO2, H/TiO2, and CQDs-H/TiO2 nanoarray samples (PDF)

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  1. Sadaf Khoomortezaei, Hossein Abdizadeh, Mohammad Reza Golobostanfard. Ferro-photocatalytic Enhancement of Photoelectrochemical Water Splitting Using the WO3/BiFeO3 Heterojunction. Energy & Fuels 2021, 35 (11) , 9623-9634.
  2. Dibyendu Ghosh, Krishnendu Roy, K. Sarkar, Pooja Devi, Praveen Kumar. Surface Plasmon-Enhanced Carbon Dot-Embellished Multifaceted Si(111) Nanoheterostructure for Photoelectrochemical Water Splitting. ACS Applied Materials & Interfaces 2020, 12 (25) , 28792-28800.
  3. Hui Luo, Stoichko Dimitrov, Matyas Daboczi, Ji-Seon Kim, Qian Guo, Yuanxing Fang, Marc-Antoine Stoeckel, Paolo Samorì, Oliver Fenwick, Ana Belen Jorge Sobrido, Xinchen Wang, Maria-Magdalena Titirici. Nitrogen-Doped Carbon Dots/TiO2 Nanoparticle Composites for Photoelectrochemical Water Oxidation. ACS Applied Nano Materials 2020, 3 (4) , 3371-3381.
  4. Georgios Zafeiropoulos, Hannah Johnson, Sachin Kinge, Mauritius C. M. van de Sanden, Mihalis N. Tsampas. Solar Hydrogen Generation from Ambient Humidity Using Functionalized Porous Photoanodes. ACS Applied Materials & Interfaces 2019, 11 (44) , 41267-41280.
  5. Fan Liao, Yandi Shi, Qian Dang, Haiwei Yang, Hui Huang, Zhenhui Kang, Mingwang Shao. Carbon dots dominated photoelectric surface in titanium dioxide nanotube/nitrogen-doped carbon dot/gold nanocomposites for improved photoelectrochemical water splitting. Journal of Colloid and Interface Science 2022, 606 , 1274-1283.
  6. Tingsheng Zhou, Lei Li, Jinhua Li, Jiachen Wang, Jing Bai, Ligang Xia, Qunjie Xu, Baoxue Zhou. Electrochemically reduced TiO2 photoanode coupled with oxygen vacancy-rich carbon quantum dots for synergistically improving photoelectrochemical performance. Chemical Engineering Journal 2021, 425 , 131770.
  7. Yidong Han, Jie Wu, Yi Li, Xiaoqing Gu, Tiwei He, Yu Zhao, Hui Huang, Yang Liu, Zhenhui Kang. Carbon dots enhance the interface electron transfer and photoelectrochemical kinetics in TiO2 photoanode. Applied Catalysis B: Environmental 2021, 48 , 120983.
  8. Dong Qiu, Chengli He, Yuxuan Lu, Qiaodan Li, Yang Chen, Xiaoli Cui. Assembling γ-graphyne surrounding TiO 2 nanotube arrays: an efficient p–n heterojunction for boosting photoelectrochemical water splitting. Dalton Transactions 2021, 50 (42) , 15422-15432.
  9. Tingsheng Zhou, Jiachen Wang, Yan Zhang, Changhui Zhou, Jing Bai, Jinhua Li, Baoxue Zhou. Oxygen vacancy-abundant carbon quantum dots as superfast hole transport channel for vastly improving surface charge transfer efficiency of BiVO4 photoanode. Chemical Engineering Journal 2021, 8 , 133414.
  10. Jiachen Wang, Tingsheng Zhou, Yan Zhang, Shuai Chen, Jing Bai, Jinhua Li, Hong Zhu, Baoxue Zhou. The design of high performance photoanode of CQDs/TiO2/WO3 based on DFT alignment of lattice parameter and energy band, and charge distribution. Journal of Colloid and Interface Science 2021, 600 , 828-837.
  11. Sheng-Mu You, Tzu-Heng Wang, Ruey-An Doong, Pierre Millet. PEC water splitting using mats of calcined TiO2 rutile nanorods photosensitized by a thin layer of Ni-benzene dicarboxylic acid MOF. Electrochimica Acta 2021, 393 , 139014.
  12. Kamalesh Debnath, Tanmoy Majumder, Suvra Prakash Mondal. Photoelectrochemical and photosensing study of nitrogen doped carbon nanoparticles sensitized TiO2 nanorods. Diamond and Related Materials 2021, 46 , 108683.
  13. Yalong Zou, Jiabo Le, Yufeng Cao, Na An, Yang Zhou, Jianming Li, Deyu Liu, Yongbo Kuang. Tetragonal tungsten bronze type Sn( ii )-based quaternary oxides: a new class of visible-light-absorbing semiconductors for photoelectrochemical water oxidation. Journal of Materials Chemistry A 2021, 9 (37) , 21085-21093.
  14. Zhao Liang, Ding Chen, Shang Xu, Zhi Fang, Lin Wang, Weiyou Yang, Huilin Hou. Synergistic promotion of photoelectrochemical water splitting efficiency of TiO 2 nanorod arrays by doping and surface modification. Journal of Materials Chemistry C 2021, 9 (36) , 12263-12272.
  15. Xiaoyun Xie, Shan Li, Kemin Qi, Zhaowei Wang. Photoinduced synthesis of green photocatalyst Fe3O4/BiOBr/CQDs derived from corncob biomass for carbamazepine degradation: The role of selectively more CQDs decoration and Z-scheme structure. Chemical Engineering Journal 2021, 420 , 129705.
  16. Hui Mao, Fangfang Zhang, Meng Du, Longjun Dai, Yongteng Qian, Huan Pang. Review on synthesis of porous TiO2-based catalysts for energy conversion systems. Ceramics International 2021, 47 (18) , 25177-25200.
  17. Xiaoqian Huang, Ruikang Zhang, Xiaoru Gao, Borong Yu, Yuanzhe Gao, Zhan-gang Han. TiO2-rutile/anatase homojunction with enhanced charge separation for photoelectrochemical water splitting. International Journal of Hydrogen Energy 2021, 46 (52) , 26358-26366.
  18. Guojun Dong, Xiang Cheng, Yingpu Bi. Hierarchical TiO 2 Photoanodes with Spatial Charge Separation for Efficient Oxygen Evolution Reaction. Solar RRL 2021, 5 (6) , 2000449.
  19. Ningchao Zheng, Xi He, Weiqing Guo, Zhuofeng Hu. Enhancement of mass transfer efficiency and photoelectrochemical activity for TiO2 nanorod arrays by decorating Ni3+-states functional NiO water oxidation cocatalyst. Chinese Chemical Letters 2021, 32 (6) , 1993-1997.
  20. Yalong Zou, Deyu Liu, Xiangrui Meng, Qitao Liu, Yang Zhou, Jianming Li, Zhiying Zhao, Ding Chen, Yongbo Kuang. Structural limiting factors of mixed-valent tin oxides in photoelectrochemical application: A comparative exploration. Journal of Energy Chemistry 2021, 56 , 504-511.
  21. Hong-Yan Wang, Rong Hu, Na Wang, Gui-Lin Hu, Kai Wang, Wei-Hua Xie, Rui Cao. Boosting Photoanodic Activity for Water Splitting in Carbon Dots Aqueous Solution without any Traditional Supporting Electrolyte. Applied Catalysis B: Environmental 2021, 103 , 120378.
  22. Liujun Hu, Hongli Yang, Shuhua Wang, Junlun Gao, Huilin Hou, Weiyou Yang. MOF-derived hexagonal In 2 O 3 microrods decorated with g-C 3 N 4 ultrathin nanosheets for efficient photocatalytic hydrogen production. Journal of Materials Chemistry C 2021, 9 (16) , 5343-5348.
  23. Jing Huang, Tao Chen, Mingyang Zhao, Ping Yi, Feifan Zhao, Bing He, Yang Wang, Yihuang Chen, Xueqin Liu, Zhen Li. Surface oxygen vacancies of TiO 2 nanorods by electron beam irradiation for efficient photoelectrochemical water splitting. CrystEngComm 2021, 23 (16) , 2952-2960.
  24. Chengkai Xia, Heng Wang, Jung Kyu Kim, Jingyu Wang. Rational Design of Metal Oxide‐Based Heterostructure for Efficient Photocatalytic and Photoelectrochemical Systems. Advanced Functional Materials 2021, 31 (12) , 2008247.
  25. Lei Jin, Haiguang Zhao, Zhiming M. Wang, Federico Rosei. Quantum Dots‐Based Photoelectrochemical Hydrogen Evolution from Water Splitting. Advanced Energy Materials 2021, 11 (12) , 2003233.
  26. Zhongrui Yu, Haobo Liu, Mingyuan Zhu, Ying Li, Wenxian Li. Interfacial Charge Transport in 1D TiO 2 Based Photoelectrodes for Photoelectrochemical Water Splitting. Small 2021, 17 (9) , 1903378.
  27. A. Ansón-Casaos, J. Hernández-Ferrer, L. Vallan, H. Xie, M. Lira-Cantú, A.M. Benito, W.K. Maser. Functionalized carbon dots on TiO2 for perovskite photovoltaics and stable photoanodes for water splitting. International Journal of Hydrogen Energy 2021, 46 (22) , 12180-12191.
  28. Yen-Linh Thi Ngo, Phi Luan Nguyen, Jayasmita Jana, Won Mook Choi, Jin Suk Chung, Seung Hyun Hur. Simple paper-based colorimetric and fluorescent glucose sensor using N-doped carbon dots and metal oxide hybrid structures. Analytica Chimica Acta 2021, 1147 , 187-198.
  29. Feng Xiao, Ruiqi Guo, Xuan He, Hui Chen, Wei Fang, Weixin Li, Huali Wang, Zhimin Sun, Pan Tian, Lei Zhao. Enhanced photocurrent by MOFs layer on Ti-doped α-Fe2O3 for PEC water oxidation. International Journal of Hydrogen Energy 2021, 46 (11) , 7954-7963.
  30. Pan Yang, Qingcui Liu, Feng Yu, Jianning Wu, Zhiyong Liu, Banghua Peng. Cobalt substituted polyoxophosphomolybdate modified TiO2 for boosted photoelectrocatalytic water oxidation. Journal of Alloys and Compounds 2021, 854 , 157232.
  31. Junqiang Han, Zhaoxia Han, Xianniu Da, Zhijin Yang, Dawei Zhang, Ruijin Hong, Chunxian Tao, Hui Lin, Yuanshen Huang. Preparation and photocatalytic activity of red light-emitting carbon dots/P25 heterojunction photocatalyst with ultra-wide absorption spectrum. Materials Research Express 2021, 8 (2) , 025002.
  32. Umairah Abd Rani, Law Yong Ng, Ching Yin Ng, Chee Sien Wong, Ebrahim Mahmoudi. Preparation of Carbon-Based Photo-catalyst for Degradation of Phenols. 2021,,, 293-323.
  33. Asad Mahmood, Gansheng Shi, Zhuang Wang, Zepeng Rao, Wang Xiao, Xiaofeng Xie, Jing Sun. Carbon quantum dots-TiO2 nanocomposite as an efficient photocatalyst for the photodegradation of aromatic ring-containing mixed VOCs: An experimental and DFT studies of adsorption and electronic structure of the interface. Journal of Hazardous Materials 2021, 401 , 123402.
  34. Dibyendu Ghosh, Krishnendu Sarkar, Pooja Devi, Ki-Hyun Kim, Praveen Kumar. Current and future perspectives of carbon and graphene quantum dots: From synthesis to strategy for building optoelectronic and energy devices. Renewable and Sustainable Energy Reviews 2021, 135 , 110391.
  35. Kaihe Zhou, Peng Li, Yanwei Zhu, Xiaming Ye, Huazhi Chen, Yueping Yang, Yangqing Dan, Yanfen Yuan, Huilin Hou. Atomic Layer Deposition of ZnO on TiO2 Nanofibers for Boosted Photocatalytic Hydrogen Production. Catalysis Letters 2021, 151 (1) , 78-85.
  36. Yuan-Chang Liang, Wei-Cheng Zhao. Morphology-dependent photocatalytic and gas-sensing functions of three-dimensional TiO 2 –ZnO nanoarchitectures. CrystEngComm 2020, 22 (44) , 7575-7589.
  37. Piotr Kupracz, Emerson Coy, Katarzyna Grochowska, Jakub Karczewski, Jakub Rysz, Katarzyna Siuzdak. The pulsed laser ablation synthesis of colloidal iron oxide nanoparticles for the enhancement of TiO2 nanotubes photo-activity. Applied Surface Science 2020, 530 , 147097.
  38. Thanh Tai Nguyen, Malkeshkumar Patel, Joondong Kim. All-inorganic metal oxide transparent solar cells. Solar Energy Materials and Solar Cells 2020, 217 , 110708.
  39. Surangkana Wannapop, Asanee Somdee. Enhanced visible light absorption of TiO2 nanorod photoanode by NiTiO3 decoration for high-performance photoelectrochemical cells. Ceramics International 2020, 46 (16) , 25758-25765.
  40. Qian Guo, Hui Luo, Jifang Zhang, Qiushi Ruan, Arun Prakash Periasamy, Yuanxing Fang, Zailai Xie, Xuanhua Li, Xinchen Wang, Junwang Tang, Joe Briscoe, Magdalena Titirici, Ana Belen Jorge. The role of carbon dots – derived underlayer in hematite photoanodes. Nanoscale 2020, 12 (39) , 20220-20229.
  41. Qi-Shi Si, Wan-Qian Guo, Hua-Zhe Wang, Bang-Hai Liu, Nan-Qi Ren. Carbon quantum dots-based semiconductor preparation methods, applications and mechanisms in environmental contamination. Chinese Chemical Letters 2020, 31 (10) , 2556-2566.
  42. Piotr Kupracz, Katarzyna Grochowska, Jakub Karczewski, Jakub Wawrzyniak, Katarzyna Siuzdak. The Effect of Laser Re-Solidification on Microstructure and Photo-Electrochemical Properties of Fe-Decorated TiO2 Nanotubes. Materials 2020, 13 (18) , 4019.
  43. Jianwu Chen, Yueping Yang, Kai Song, Shang Xu, Tian Zhang, Huilin Hou. Deposition of a ZnO Nanolayer on TiO 2 Nanorods Nanoarrays with Tailored Thickness towards Boosted Photoelectrochemical Hydrogen Production Activity. ChemistrySelect 2020, 5 (31) , 9893-9898.
  44. Huilin Hou, Yanfen Yuan, Sheng Cao, Yueping Yang, Xiaming Ye, Weiyou Yang. CuInS 2 nanoparticles embedded in mesoporous TiO 2 nanofibers for boosted photocatalytic hydrogen production. Journal of Materials Chemistry C 2020, 8 (32) , 11001-11007.
  45. Tingsheng Zhou, Shuai Chen, Linsen Li, Jiachen Wang, Yan Zhang, Jinhua Li, Jing Bai, Ligang Xia, Qunjie Xu, Mohammadi Rahim, Baoxue Zhou. Carbon quantum dots modified anatase/rutile TiO2 photoanode with dramatically enhanced photoelectrochemical performance. Applied Catalysis B: Environmental 2020, 269 , 118776.
  46. Hui Luo, Qian Guo, Petra Ágota Szilágyi, Ana Belen Jorge, Maria-Magdalena Titirici. Carbon Dots in Solar-to-Hydrogen Conversion. Trends in Chemistry 2020, 2 (7) , 623-637.
  47. Liqun Wang, Wenping Si, Yueyu Tong, Feng Hou, Daniele Pergolesi, Jungang Hou, Thomas Lippert, Shi Xue Dou, Ji Liang. Graphitic carbon nitride (g‐C 3 N 4 )‐based nanosized heteroarrays: Promising materials for photoelectrochemical water splitting. Carbon Energy 2020, 2 (2) , 223-250.
  48. Anu Babusenan, B. Pandey, Somnath C. Roy, Jayeeta Bhattacharyya. Charge transfer mediated photoluminescence enhancement in carbon dots embedded in TiO2 nanotube matrix. Carbon 2020, 161 , 535-541.
  49. Asad Mahmood, Xiao Wang, Gansheng Shi, Zhuang Wang, Xiaofeng Xie, Jing Sun. Revealing adsorption and the photodegradation mechanism of gas phase o-xylene on carbon quantum dots modified TiO2 nanoparticles. Journal of Hazardous Materials 2020, 386 , 121962.
  50. Mária Kováčová, Eva Špitalská, Zoran Markovic, Zdenko Špitálský. Carbon Quantum Dots As Antibacterial Photosensitizers and Their Polymer Nanocomposite Applications. Particle & Particle Systems Characterization 2020, 37 (1) , 1900348.
  51. Ting Li, Dongyan Ding. Enhanced Photoelectrochemical Water Splitting Performance of Ni/Si-doped TiO 2 Photoanode Fabricated through Electrochemical Reduction in Aqueous Solutions. Journal of The Electrochemical Society 2020, 167 (6) , 066514.
  52. Ting Li, Dongyan Ding. Ni/Si-Codoped TiO2 Nanostructure Photoanode for Enhanced Photoelectrochemical Water Splitting. Materials 2019, 12 (24) , 4102.